CN109967117B - Preparation method of modified Y-type molecular sieve - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 130
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 238000009826 distribution Methods 0.000 claims abstract description 28
- 230000032683 aging Effects 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 238000004537 pulping Methods 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- 238000001069 Raman spectroscopy Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- 239000002149 hierarchical pore Substances 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005216 hydrothermal crystallization Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 17
- 238000005336 cracking Methods 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 12
- 238000004523 catalytic cracking Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- -1 carbonium ion Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
A preparation method of a modified Y-type molecular sieve is characterized by comprising the steps of obtaining a NaY molecular sieve filter cake, adding water again to the filter cake for pulping, adding an aluminum source and an alkali solution for gelling reaction, aging a silicon source, and placing the aged slurry in a closed reaction kettle for hydrothermal crystallization. The modified Y-type molecular sieve obtained by the method of the invention has the advantages that the corrugated mesoporous structure is uniformly coated on the surface of the crystal grain of the Y-type molecular sieve, the particle size distribution is uniform, the surface mesoporous structure is smooth, and the pore channel distribution presents the characteristic of gradient distribution.
Description
Technical Field
The invention relates to a preparation method of a modified Y-type molecular sieve, in particular to a preparation method of a modified Y-type molecular sieve which grows a mesoporous layer on the surface of a molecular sieve grain and coats the surface of the molecular sieve grain.
Background
Catalytic cracking is an important process in petroleum refining, is widely applied to the petroleum processing industry, and plays a significant role in oil refineries. In the catalytic cracking process, heavy fractions such as vacuum distillates or residues of heavier components are reacted in the presence of a catalyst to convert into gasoline, distillates and other liquid cracked products and lighter gaseous cracked products of four carbons or less. The catalytic cracking reaction process follows a carbonium ion reaction mechanism, and therefore, an acidic catalytic material, particularly a catalytic material having a strong B acid center, needs to be used. Amorphous alumino-silicate material is an acidic catalytic material, which has both B and L acid centers, is the main active component in early catalytic cracking catalysts, but is gradually replaced by crystalline molecular sieves due to its lower cracking activity and higher required reaction temperature. Crystalline molecular sieves are porous materials with a pore size of less than 2nm and a special crystalline phase structure, and materials with a pore size of less than 2nm are named as microporous materials according to the definition of IUPAC, so that crystalline molecular sieves or zeolites generally belong to microporous materials, and the microporous molecular sieve materials have stronger acidity and higher structural stability due to complete crystal structures and special framework structures, show higher catalytic activity in catalytic reactions, and are widely applied to petroleum processing and other catalytic industries.
The Y-type molecular sieve is used as a typical microporous molecular sieve material, and is applied in the fields of catalytic cracking, hydrocracking and the like on a large scale due to the regular pore channel structure, good stability and strong acidity. When the modified Y-type molecular sieve is used in a catalytic cracking catalyst, certain modification treatment is usually required to be carried out on the Y-type molecular sieve, such as skeleton dealumination inhibition through rare earth modification, the structural stability of the molecular sieve is improved, the retention degree of acid centers is increased, and the cracking activity is further improved; or the framework silicon-aluminum ratio is improved through ultra-stabilization treatment, so that the stability of the molecular sieve is improved.
Along with the increasing exhaustion of petroleum resources, the trend of crude oil heaving and deterioration is obvious, the slag blending proportion is continuously improved, and the requirement of the market for light oil products is not reduced, so that in recent years, the deep processing of heavy oil and residual oil is more and more emphasized in the petroleum processing industry, a plurality of refineries begin to blend vacuum residual oil, even normal pressure residual oil is directly used as a cracking raw material, the catalytic cracking of heavy oil gradually becomes a key technology for improving economic benefits of oil refining enterprises, and the macromolecular cracking capability of a catalyst therein is a focus of attention. The Y-type molecular sieve is the most main cracking active component in the conventional cracking catalyst, but due to the smaller pore channel structure, the Y-type molecular sieve shows a relatively obvious pore channel limiting effect in macromolecular reaction, and also shows a certain inhibiting effect on the cracking reaction of macromolecules such as heavy oil or residual oil and the like. Therefore, for catalytic cracking of heavy oil, it is necessary to use a material having a large pore size, no diffusion limitation to reactant molecules, and a high cracking activity.
According to the IUPAC definition, a material with a pore size of 2-50 nm is a mesoporous (mesoporous) material, and the size range of macromolecules such as heavy oil or residual oil is in the pore size range, so that the research of mesoporous materials, particularly mesoporous silicon-aluminum materials, has attracted great interest to researchers in the catalysis field. Mesoporous materials are firstly developed and succeeded by Mobil Corporation in 1992 (Beck J S, Vartuli J Z, Roth W J et al, J.Am.Chem.Comm.Soc., 1992, 114, 10834-containing 10843) and named as M41S series mesoporous molecular sieves, including MCM-41(Mobil Corporation Material-41) and MCM-48, etc., wherein the pore diameter of the molecular sieves can reach 1.6-10 nm, and the mesoporous materials are uniform and adjustable, have concentrated pore diameter distribution, large specific surface area and pore volume and strong adsorption capacity; however, the pore wall structure of the molecular sieve is an amorphous structure, so that the molecular sieve has poor hydrothermal stability and weak acidity, cannot meet the operation conditions of catalytic cracking, and is greatly limited in industrial application.
In order to solve the problem of poor hydrothermal stability of mesoporous molecular sieves, part of research work focuses on increasing the thickness of the pore walls of the molecular sieves, and if a neutral template agent is adopted, the molecular sieve with thicker pore walls can be obtained, but the defect of weaker acidity still exists. In CN 1349929a, a novel mesoporous molecular sieve is disclosed, in which primary and secondary structural units of zeolite are introduced into the pore walls of the molecular sieve, so that the molecular sieve has the basic structure of the conventional zeolite molecular sieve, and the mesoporous molecular sieve has strong acidity and ultrahigh hydrothermal stability. However, the molecular sieve has the defects that a template agent with high price is required to be used, the aperture is only about 2.7nm, the molecular sieve still has large steric hindrance effect on macromolecular cracking reaction, the structure is easy to collapse under the high-temperature hydrothermal condition, and the cracking activity is poor.
In the field of catalytic cracking, silicon-aluminum materials are widely used due to their strong acid centers and good cracking properties. The proposal of the mesoporous concept provides possibility for the preparation of a novel catalyst, and the current research results mostly focus on the use of expensive organic template and organic silicon source, and mostly need to be subjected to a high-temperature hydrothermal post-treatment process. In order to reduce the preparation cost and obtain the porous in the mesoporous rangeMaterials, more research efforts have focused on the development of disordered mesoporous materials. US5,051,385 discloses a monodisperse mesoporous silicon-aluminum composite material, which is prepared by mixing acidic inorganic aluminum salt and silica sol and then adding alkali for reaction, wherein the aluminum content is 5-40 wt%, the aperture is 20-50 nm, and the specific surface area is 50-100 m2(ii) in terms of/g. US4,708,945 discloses a catalyst prepared by loading silica particles or hydrated silica on porous boehmite and hydrothermally treating the obtained composite at a temperature of more than 600 ℃ for a certain time to obtain a catalyst prepared by loading silica on the surface of the boehmite, wherein the silica is combined with hydroxyl of the transition boehmite and the surface area reaches 100-200 m2(iv) g, average pore diameter of 7 to 7.5 nm. A series of acidic cracking catalysts are disclosed in US4,440,872, some of which are supported on gamma-Al2O3Impregnating silane, and then roasting at 500 ℃ or treating with water vapor. In CN1353008A, inorganic aluminum salt and water glass are used as raw materials, stable and clear silicon-aluminum sol is formed through the processes of precipitation, washing, dispergation and the like, white gel is obtained through drying, and then the silicon-aluminum catalytic material is obtained through roasting for 1-20 hours at 350-650 ℃. CN1565733A discloses a mesoporous silicon-aluminum material which has a pseudo-boehmite structure, concentrated pore size distribution and a specific surface area of about 200-400 m2The mesoporous silicon-aluminum material has the advantages that the pore volume is 0.5-2.0 ml/g, the average pore diameter is 8-20 nm, the most probable pore diameter is 5-15 nm, an organic template agent is not needed in the preparation of the mesoporous silicon-aluminum material, the synthesis cost is low, the obtained silicon-aluminum material has high cracking activity and hydrothermal stability, and the high macromolecular cracking performance is shown in a catalytic cracking reaction.
Disclosure of Invention
Through a large number of experiments, the inventor of the invention discovers that a mesoporous layer with a pseudo-boehmite structure is grown on the surface of the Y-type molecular sieve by an attached crystal growth method through a secondary hydrothermal crystallization process and is coated on the surface of the molecular sieve, the mesoporous layer and the molecular sieve are mutually connected through bonding, and the granularity is more uniform. Based on this, the present invention was made.
The modified Y-type molecular sieve prepared by the method has a mesoporous layer with larger pore diameter, can form continuous through pore channels and acid centers with gradient distribution, respectively strengthens the respective advantages of a micropore and a mesoporous structure, and maximally promotes macromolecular reaction.
The preparation method provided by the invention is characterized by comprising the following steps: (a) preparing raw materials capable of synthesizing a NaY molecular sieve, uniformly mixing, and then statically crystallizing for 8-50 hours at the temperature of 95-105 ℃; (b) filtering and washing the slurry obtained by crystallization to obtain a NaY molecular sieve filter cake; (c) adding water into the NaY molecular sieve filter cake again for pulping, homogenizing, adding an aluminum source and an alkali solution simultaneously at the temperature of 30-70 ℃ under vigorous stirring for gelling reaction, and controlling the pH value of slurry in the gelling process to be 9-11; (d) according to the weight of alumina in the aluminum source and alkali solution, according to SiO2:Al2O3Adding a silicon source into the gel-forming slurry according to the weight ratio of (1-6), and aging at the temperature of 30-90 ℃ for 1-4 hours; (e) and (3) placing the aged slurry into a closed reaction kettle, crystallizing for 3-30 hours at the temperature of 95-105 ℃, and recovering the product.
In the preparation method provided by the invention, the raw materials for synthesizing the NaY molecular sieve in the step (a) are usually directing agent, water glass, sodium metaaluminate, aluminum sulfate and deionized water, and the adding proportion of the raw materials can be the charging proportion of the conventional NaY molecular sieve, for example, Na can be added2O：Al2O3：SiO2：H2O is 1.5-8: 1: 5-18: 100 to 500, the charge ratio of NaY molecular sieve for preparing special performance, for example, the charge ratio of NaY molecular sieve for preparing large or small crystal grains, is not particularly limited as long as NaY molecular sieve having FAU crystal phase structure can be obtained. The guiding agent can be prepared according to the prior art (US3639099 and US3671191), and the guiding agent is prepared by mixing a silicon source, an aluminum source, alkali liquor and deionized water according to (15-18) Na2O:Al2O3:(15～17)SiO2:(280～380)H2Mixing the components according to the molar ratio of O, uniformly stirring, and standing and aging for 0.5-48 h at room temperature to 70 ℃. In the NaY molecular sieveIn the feeding proportion of (A), Al in the guiding agent2O3The content of (A) is based on the total charge Al2O33 to 15%, preferably 5 to 10% of the total amount. The static crystallization in the step (a) is carried out for 8 to 50 hours, preferably 10 to 40 hours, and more preferably 15 to 35 hours.
The invention provides the preparation method, wherein, the aluminum source in the step (c) is selected from one or more of aluminum nitrate, aluminum sulfate or aluminum chloride; the alkali solution is selected from one or more of ammonia water, potassium hydroxide, sodium hydroxide or sodium metaaluminate. When sodium metaaluminate is used as the alkali solution, the alumina content is counted in the total alumina content. The gelling reaction is carried out at the temperature of 30-70 ℃, preferably 35-65 ℃.
In the preparation method provided by the invention, the silicon source in the step (d) is one or more selected from water glass, sodium silicate, tetraethoxysilane and silicon oxide. The aging is carried out at the temperature of 30-90 ℃, preferably at the temperature of 40-80 ℃.
In the preparation method provided by the invention, the crystallization process in the step (e) is a crystallization process under a hydrothermal condition in a closed reaction kettle, a static crystallization process or a dynamic crystallization process can be selected, and the hydrothermal crystallization time is 3-30 hours, preferably 5-25 hours. Said recovery usually comprises the steps of filtration, washing and drying, well known to the person skilled in the art and not described in more detail here.
The modified Y-type molecular sieve prepared by the method has the advantages that the microporous molecular sieve has complete crystal structure, strong acidity, excellent structural stability and high catalytic activity, and a mesoporous layer with smooth pore passage, small diffusion resistance and larger pore diameter is grafted and grown on the surface of the microporous molecular sieve. The FAU crystal phase structure in the scanning electron microscope is represented as a regular octahedron or sheet structure, and the pseudo-boehmite structure is represented as a wrinkled structure. The preparation method builds the micropore and the mesoporous structure together to form a continuous through pore canal and an acid center with gradient distribution, respectively strengthens the respective advantages of the two structures, and maximally promotes macromolecular reaction. The mesoporous structure grows on the surface of the molecular sieve crystal grain and coats the NaY molecular sieve crystal grain, the particle size distribution is more uniform, and the particle size is 1-2 mu m as shown by a scanning electron microscope. The Y-type molecular sieve is coated with the wrinkled mesoporous silicon-aluminum layer to form a composite structure with organically combined micropores and mesopores.
The modified Y-type molecular sieve prepared by the method has XRD spectrums with diffraction peaks at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees, 28 degrees, 31.4 degrees, 38.5 degrees, 49 degrees and 65 degrees respectively. Wherein, the characteristic diffraction peaks appearing at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 ° and 31.4 ° in the XRD spectrogram correspond to the FAU crystal phase structure of the Y-type molecular sieve; characteristic diffraction peaks appearing at 28 °, 38.5 °, 49 ° and 65 ° in the XRD spectrum correspond to the pseudo-boehmite structure.
The modified Y-type molecular sieve prepared by the method has an a/b value of 1.2-9.5 in a Raman (Raman) spectrum, wherein a is a displacement of 500cm in the Raman (Raman) spectrum-1B is a shift of 350cm-1Spectral peak intensity of (a).
The surface silicon-aluminum atomic ratio of the modified Y-type molecular sieve prepared by the method is 0.25-1.5, which is measured by an XPS method; the total specific surface area is 350-650 m2The mesoporous specific surface area is 50-400 m2(ii)/g; the modified Y-type molecular sieve prepared by the method of the invention presents several pore distributions and multistage pore distribution characteristics respectively at about 3.8nm, 11nm and 60 nm.
Drawings
FIG. 1 is an SEM scanning electron micrograph of the modified Y-type molecular sieve prepared by the preparation method of the invention.
FIG. 2 is an SEM scanning electron micrograph of a typical NaY molecular sieve.
FIG. 3 is an X-ray diffraction pattern of the modified Y-type molecular sieve obtained by the preparation method of the present invention.
FIG. 4 is a BJH pore size distribution curve of the modified Y-type molecular sieve obtained by the preparation method of the invention.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The SEM was a Hitachi S4800 field emission SEM, Japan, with an accelerating voltage of 5kV, and the spectra were collected and processed with Horiba 350 software.
The phase of the sample was determined by X-ray diffraction.
The physicochemical data of the specific surface, the pore structure and the like of the sample are measured by adopting a low-temperature nitrogen adsorption-desorption method.
The chemical composition of the mesoporous layer is determined by X-ray photoelectron spectroscopy.
The laser Raman spectrum adopts a LabRAM HR UV-NIR type laser confocal Raman spectrometer of HORIBA company of Japan, the wavelength of an excitation light source is 325nm, an ultraviolet 15-time objective lens, a confocal pinhole is 100 mu m, and the spectrum scanning time is 100 s.
Example 1
This example illustrates the preparation of the modified Y-type molecular sieve provided by the present invention.
Under the condition of vigorous stirring, water glass, aluminum sulfate, sodium metaaluminate, guiding agent and deionized water are mixed according to 8.5SiO2：Al2O3：2.65Na2O：210H2Mixing the molar ratio of O to prepare NaY molecular sieve gel, wherein the mass ratio of the guiding agent is 5%, stirring for 1 hour at room temperature, placing the gel in a crystallization kettle for static crystallization treatment for 30 hours at 100 ℃, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; adding water again into the obtained NaY molecular sieve filter cake for pulping, homogenizing, and adding AlCl at 45 deg.C under vigorous stirring3Solution (concentration 60 gAl)2O3/L) and NaAlO2Solution (concentration 102 gAl)2O3/L) adding the mixture at the same time to carry out gelling reaction, controlling the pH value of the slurry to be 10.0 in the gelling process, and adding the mixture for a certain time according to the used AlCl3Solution and NaAlO2Total Al in solution2O3By weight, in terms of SiO2:Al2O31:1.8 weight ratio, the desired water glass solution (concentration 125 gSiO)2/L) adding into the gel-forming slurry, aging at 55 deg.C for 3 hr, placing the slurry into a stainless steel reaction kettle, crystallizing at 100 deg.C for 20 hr, filtering, washing, and drying at 120 deg.C to obtain modified YType molecular sieve, noted SAY-1.
SAY-1, and a typical NaY molecular sieve, wherein the SEM image is shown in FIG. 2, the comparison shows that SAY-1 has uniform particle size distribution, particle size of 1-2 μm, and a wrinkled structure on the surface, indicating that the mesoporous structure grows on the surface of the NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum thereof is as shown in fig. 3, and diffraction peaks appear at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 °, 28 °, 31.4 °, 38.5 °, 49 ° and 65 °, wherein the characteristic diffraction peak marked ≧ corresponds to the FAU crystal phase structure of the Y-type molecular sieve, and the characteristic diffraction peak marked # corresponds to the pseudo-boehmite structure.
SAY-1, wherein a is a shift of 500cm in the Raman (Raman) spectrum-1B is a shift of 350cm-1(ii) spectral peak intensity of; the surface silicon-aluminum atomic ratio measured by the XPS method was 0.74.
SAY-1, as shown in FIG. 4, exhibits multistage pore distribution characteristics, and several pore distributions at 3.8nm, 11nm and 60nm, respectively, and a total specific surface area of 644m2(g) the mesoporous specific surface area is 65m2/g。
Example 2
This example illustrates the preparation of the modified Y-type molecular sieve provided by the present invention.
The preparation of NaY molecular sieve is the same as example 1 except that the crystallization treatment time is 46 hours; pulping the obtained NaY molecular sieve filter cake with water, homogenizing, and adding Al (NO) at 30 deg.C under vigorous stirring3)3Solution (concentration 60 gAl)2O3L) and sodium hydroxide (concentration 1M) are simultaneously subjected to gelling reaction, the pH value of slurry in the gelling process is controlled to be 10.8, and after a certain time, Al (NO) is added according to the use3)3Al of solution2O3By weight, in terms of SiO2:Al2O3Adding the required tetraethoxysilane into the gel-forming slurry according to the weight ratio of 1:4, aging at 60 ℃ for 4 hours, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 14 hours, filtering, washing and drying at 120 ℃ to obtain the modified silicon dioxideY type molecular sieve, noted as SAY-2.
SAY-2 scanning electron microscope photo has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure.
SAY-2, has an a/b of 1.3, and has a surface silicon-aluminum atomic ratio of 0.41 as measured by XPS method.
SAY-2 has the characteristics shown in FIG. 4, presents a multistage pore distribution, and has a total specific surface area of 420m2Per g, the mesoporous specific surface area is 378m2/g。
Example 3
This example illustrates the preparation of the modified Y-type molecular sieve and the product characteristics of the modified Y-type molecular sieve provided by the present invention.
Under the condition of vigorous stirring, water glass, aluminum sulfate, sodium metaaluminate, guiding agent and deionized water are mixed according to 7.5SiO2：Al2O3：2.15Na2O：190H2Mixing the molar ratio of O to prepare NaY molecular sieve gel, wherein the mass ratio of the guiding agent is 5%, stirring for 1 hour at room temperature, placing the gel in a crystallization kettle for static crystallization treatment for 35 hours at 100 ℃, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; adding water again into the obtained NaY molecular sieve filter cake for pulping, homogenizing, and stirring at 55 deg.C under vigorous stirring to obtain Al2(SO4)3Solution (concentration 90 gAl)2O3/L) and ammonia water are added simultaneously to carry out gelling reaction, the pH value of slurry in the gelling process is controlled to be 9.0, and after a certain time, Al is added according to the use2(SO4)3Al of solution2O3By weight, in terms of SiO2:Al2O3Adding the required tetraethoxysilane into the gel-forming slurry according to the weight ratio of 1:2.2, aging at 80 ℃ for 2 hours, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 9 hours, filtering, washing and drying at 120 ℃ to obtain the modified Y-type molecular sieve which is recorded as SAY-3.
SAY-3 scanning electron microscope photo has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure.
SAY-3, has an a/b of 3.4, and has a surface silicon to aluminum atomic ratio of 0.52 as measured by XPS.
SAY-3 has the characteristics shown in FIG. 4, presents a multistage pore distribution, and has a total specific surface area of 542m2Per g, the mesoporous specific surface area is 154m2/g。
Example 4
This example illustrates the preparation of the modified Y-type molecular sieve and the product characteristics of the modified Y-type molecular sieve provided by the present invention.
The preparation of NaY molecular sieve is the same as example 3, except that the crystallization treatment time is 42 hours; adding water again into the obtained NaY molecular sieve filter cake for pulping, homogenizing, and then stirring vigorously at room temperature to obtain AlCl3Adding the solution and sodium hydroxide solution simultaneously to carry out gelling reaction, controlling the pH value of the slurry to be 9.6 in the gelling process, and adding AlCl according to the use after a certain time3Al of solution2O3By weight, in terms of SiO2:Al2O3Adding the required water glass solution into the gel-forming slurry according to the weight ratio of 1:1.2, aging at 70 ℃ for 1 hour, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 18 hours, filtering, washing and drying at 120 ℃ to obtain the modified Y-type molecular sieve which is recorded as SAY-4.
SAY-4 has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure.
SAY-4, has an a/b of 6.0, and has a surface silicon-aluminum atomic ratio of 1.02 as measured by XPS method.
SAY-4 has the characteristic shown in FIG. 4, and shows multi-level poresDistribution characteristic, total specific surface area 575m2(g) the mesoporous specific surface area is 80m2/g。
Example 5
This example illustrates the preparation of the modified Y-type molecular sieve and the product characteristics of the modified Y-type molecular sieve provided by the present invention.
The preparation of NaY molecular sieve is the same as that of example 1, except that the crystallization treatment time is 26 hours; adding water again into the obtained NaY molecular sieve filter cake for pulping, homogenizing, and stirring at 60 deg.C under vigorous stirring to obtain Al2(SO4)3Adding the solution and ammonia water simultaneously to carry out gelling reaction, controlling the pH value of the slurry to be 9.4 in the gelling process, and adding Al according to the used Al after a certain time2(SO4)3Al of solution2O3By weight, in terms of SiO2:Al2O3Adding the required water glass solution into the gel-forming slurry according to the weight ratio of 1:1.5, aging at 60 ℃ for 1.5 hours, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 25 hours, filtering, washing and drying at 120 ℃ to obtain the modified Y-type molecular sieve which is recorded as SAY-5.
SAY-5 scanning electron microscope photo has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure.
SAY-5, has an a/b of 1.5, and has a surface silicon-aluminum atomic ratio of 0.88 as measured by XPS method.
SAY-5 has the characteristics shown in FIG. 4, presents a multi-level pore distribution, and has a total specific surface area of 398m2(g) the mesoporous specific surface area is 285m2/g。
Example 6
This example illustrates the preparation of the modified Y-type molecular sieve and the product characteristics of the modified Y-type molecular sieve provided by the present invention.
The preparation of NaY molecular sieve is the same as example 3, except that the crystallization treatment time is 30 hours; adding the obtained NaY molecular sieve filter cake againPulping with water, homogenizing, and stirring at 40 deg.C to obtain Al powder2(SO4)3Solution and NaAlO2Adding the solution at the same time to carry out gelling reaction, controlling the pH value of the slurry to be 10.2 in the gelling process, and adding Al according to the used Al after a certain time2(SO4)3Solution and NaAlO2Total Al of solution2O3By weight, in terms of SiO2:Al2O3Adding the required water glass solution into the gel-forming slurry according to the weight ratio of 1:2.6, aging at 75 ℃ for 3 hours, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 4 hours, filtering, washing and drying at 120 ℃ to obtain the modified Y-type molecular sieve which is recorded as SAY-6.
SAY-6, the scanning electron micrograph has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and coats the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure.
SAY-6, has an a/b of 2.6, and has a surface silicon-aluminum atomic ratio of 0.50 as measured by XPS method.
SAY-6 has the characteristics shown in FIG. 4, presents a multistage pore distribution, and has a total specific surface area of 532m2(iv)/g, mesoporous specific surface area is 209m2/g。
Example 7
This example illustrates the preparation of the modified Y-type molecular sieve and the product characteristics of the modified Y-type molecular sieve provided by the present invention.
The preparation of NaY molecular sieve is the same as example 1 except that the crystallization treatment time is 40 hours; adding water again into the obtained NaY molecular sieve filter cake, pulping, homogenizing, and stirring vigorously at room temperature to obtain Al (NO)3)3Solution and NaAlO2Adding the solution at the same time to carry out gelling reaction, controlling the pH value of the slurry to be 10.5 in the gelling process, and adding Al (NO) according to the use after a certain time3)3Solution and NaAlO2Total Al of solution2O3By weight, in terms of SiO2:Al2O31:5.2 by weight ratio ofAdding tetraethoxysilane into the gelling slurry, aging at 65 ℃ for 4 hours, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 30 hours, filtering, washing and drying at 120 ℃ to obtain the modified Y-type molecular sieve, which is recorded as SAY-7.
SAY-7 scanning electron microscope photo has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure.
SAY-7, has an a/b of 1.4, and has a surface silicon-aluminum atomic ratio of 0.29 as measured by XPS method.
SAY-7 has the characteristics shown in FIG. 4, presents a multistage pore distribution, and has a total specific surface area of 457m2Per g, the mesoporous specific surface area is 381m2/g。
Example 8
This example illustrates the preparation of the modified Y-type molecular sieve and the product characteristics of the modified Y-type molecular sieve provided by the present invention.
The preparation of NaY molecular sieve is the same as example 3, except that the crystallization treatment time is 38 hours; pulping the obtained NaY molecular sieve filter cake with water, homogenizing, and adding Al (NO) at 50 deg.C under vigorous stirring3)3Adding the solution and sodium hydroxide solution simultaneously to carry out gelling reaction, controlling pH of the slurry to 9.3 during gelling, adding for a certain time, and adjusting Al (NO) according to the amount of Al used3)3Al of solution2O3By weight, in terms of SiO2:Al2O3Adding the required tetraethoxysilane into the gel-forming slurry according to the weight ratio of 1:1, aging at 50 ℃ for 2 hours, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 15 hours, filtering, washing and drying at 120 ℃ to obtain the modified Y-type molecular sieve which is recorded as SAY-8.
SAY-8 scanning electron microscope photo has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure.
SAY-8, and a/b is 9.1, and the surface silicon-aluminum atomic ratio measured by XPS method is 1.30.
SAY-8 has the characteristics shown in FIG. 4, and shows a multistage pore distribution with a total specific surface area of 613m2(g) the mesoporous specific surface area is 53m2/g。
Claims (9)
1. A preparation method of a modified Y-type molecular sieve is characterized by comprising the following steps: (a) preparing raw materials for synthesizing the NaY molecular sieve, uniformly mixing, and then statically crystallizing for 8-50 hours at the temperature of 95-105 ℃; (b) filtering and washing slurry obtained by static crystallization to obtain a NaY molecular sieve filter cake; (c) adding water into the NaY molecular sieve filter cake again for pulping, homogenizing, adding an aluminum source and an alkali solution simultaneously at the temperature of 30-70 ℃ under vigorous stirring for gelling reaction, and controlling the pH value of slurry in the gelling process to be 9-11; (d) according to the weight of alumina in the aluminum source and alkali solution, according to SiO2:Al2O3Adding a silicon source into the gel-forming slurry according to the weight ratio of (1-6), and aging at the temperature of 30-90 ℃ for 1-4 hours; (e) and (3) placing the aged slurry into a closed reaction kettle, crystallizing for 3-30 hours at the temperature of 95-105 ℃, and recovering the product.
2. The method according to claim 1, wherein the aluminum source in step (c) is one or more selected from the group consisting of aluminum nitrate, aluminum sulfate and aluminum chloride; the alkali solution is selected from one or more of ammonia water, potassium hydroxide and sodium hydroxide, or the alkali is replaced by sodium metaaluminate.
3. A process as claimed in claim 2, wherein in step (c) when the alkali is replaced by sodium metaaluminate, the alumina content is calculated to the total alumina content.
4. The process according to claim 1, wherein the gelling reaction in step (c) is carried out at a temperature of from 30 ℃ to 70 ℃.
5. The method according to claim 1, wherein the silicon source in the step (d) is one or more selected from the group consisting of water glass, sodium silicate, tetraethoxysilane, tetramethoxysilane and silicon oxide.
6. The method according to claim 1, wherein the aging in the step (d) is carried out at a temperature of 40 ℃ to 80 ℃.
7. The method according to claim 1, wherein the silicon-aluminum mesoporous layer is grown on the surface of the Y-type molecular sieve crystal grains through a crystal attachment growth process.
8. The preparation method according to claim 1, wherein in the modified Y-type molecular sieve, a mesoporous structure grows on the surface of a molecular sieve grain and coats the molecular sieve grain, and the particle size is 1-2 μm as shown by a scanning electron microscope; diffraction peaks appear at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 °, 28 °, 31.4 °, 38.5 °, 49 ° and 65 ° in an XRD spectrogram respectively; the a/b is 1.2-9.5, wherein a is the shift of 500cm in Raman (Raman) spectrum-1B is a shift of 350cm-1(ii) spectral peak intensity of; the surface silicon-aluminum atomic ratio measured by an XPS method is 0.25-1.5; the total specific surface area is 350-650 m2The mesoporous specific surface area is 30-400 m2/g。
9. The method according to claim 1, wherein the modified Y-type molecular sieve has a hierarchical pore distribution characteristic in which pores are distributed at 3.8nm, 11nm and 60nm, respectively.
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